Construction of carbon pi-space by organic synthesis

2012 Fiscal Year Final Research Report

• Project Area: Emergence of highly elaborated pai-space and its function
• Project/Area Number: 20108005
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Institute for Molecular Science
• Principal Investigator: SAKURAI Hidehiro 分子科学研究所, 分子スケールナノサイエンスセンター, 准教授 (00262147)
• Project Period (FY): 2008 – 2012
• Keywords: 3次元キラルπ空間 / C3対称キラリティ / カップ構造 / スマネン / バッキーボウル / 官能化バッキーボウル / 窒素ドープ

Research Abstract

A new concept to construct versatile carbon pi-spaces is proposed based on the bottom-up approach using buckybowls as a motif. To realize this approach, chirality control and the position-specific introduction of the heteroatoms such as nitrogen into the buckybowl framework are required although these methods have been recognized to be difficult. In this project, we succeeded for the first time in developing their methodology by the modification of the synthetic route to sumanene, one of the representative buckybowls, with development of the new catalysts.

Research Products

• [Journal Article] The Synthesis of Hexaflorosumanene and its Congeners (2013)
  • Author(s): B. M. Schmidt, B. Topolinski, S. Higashibayashi, T. Kojima, M. Kawano, D. Lentz, H. Sakurai
  • Journal Title: Chem. Eur. J Volume: 19 Pages: 3282-3286
  • DOI: DOI:10.1002/chem.201204622
  • Peer Reviewed
• [Journal Article] Electonic Properties of Trifluoromethylated Corannulenes (2012)
  • Author(s): B. M. Schmidt, S. Seki, B. Topolinski, K. Ohkubo, S. Fukuzumi, H. Sakurai, D Lentz
  • Journal Title: Angew. Chem. Int. Ed Volume: 51 Pages: 11385-11388
  • DOI: DOI:10.1002/anie.201205757
  • Peer Reviewed
• [Journal Article] Emission Amplification by Sumanene Nanocrystals in an Onigiri-Type Organic-Organic Assembly (2012)
  • Author(s): Y. Morita, S. Nakao, S. Haesuwannakij, S. Higashibayashi, H. Sakurai
  • Journal Title: Chem. Commun Volume: 48 Pages: 9050-9052
  • DOI: DOI:10.1039/C2CC33643J
  • Peer Reviewed
• [Journal Article] Enantioselective synthesis of a chiral nitrogen-doped buckybowl (2012)
  • Author(s): Q.-T. Tan, S. Higashibayashi, S. Karanjit, H Sakurai
  • Journal Title: Nat. Commun Volume: 3 Pages: 891
  • DOI: DOI:10.1038/ncomms1896
  • Peer Reviewed
• [Journal Article] Trimethylsumanene: Enantioselective Synthesis, Substituent Effect on Bowl Structure, Inversion Energy, and Electron Conductivity (2012)
  • Author(s): S. Higashibayashi, R. Tsuruoka, Y. Soujanya, U. Purushotham, G. N. Sastry, S. Seki, T. Ishikawa, S. Toyota, H. Sakurai
  • Journal Title: Bull. Chem. Soc. Jpn Volume: 85 Pages: 450-467
  • DOI: DOI:10.1246/bcsj.20110286
  • Peer Reviewed
• [Journal Article] Selective Synthesis of C_3 Symmetric Functionalized Sumanenes (2012)
  • Author(s): S. Higashibayashi, Nasir Baig R. B., Y. Morita, H. Sakurai
  • Journal Title: Chem. Lett Volume: 41 Pages: 84-86
  • DOI: DOI:10.1246/cl.2012.84
  • Peer Reviewed
• [Journal Article] Optical Resolution of Chiral Buckybowls by Chiral HPLC (2010)
  • Author(s): R. Tsuruoka, S. Higashibayashi, T. Ishikawa, S. Toyota, H. Sakurai
  • Journal Title: Chem. Lett Volume: 39 Pages: 646-647
  • DOI: DOI:10.1246/cl.2010.646
  • Peer Reviewed
• [Journal Article] Preparation of C_3 Symmetric Homochiral syn-Trisnorbornabenzenes through Regio-selective Cyclotrimerization of Enantiopure Iodonorbornenes (2009)
  • Author(s): A. F. G. Masud Reza, S. Higashibayashi, H. Sakurai
  • Journal Title: Chem. Asian J Volume: 4 Pages: 1329-1337
  • DOI: DOI:10.1002/asia.200900132
  • Peer Reviewed
• [Journal Article] Asymmetric Synthesis of a Chiral Buckybowl, Trimethylsumanene (2008)
  • Author(s): S. Higashibayashi, H. Sakurai
  • Journal Title: J. Am. Chem. Soc Volume: 130 Pages: 8592-8593
  • DOI: DOI:10.1021/ja802822k
  • Peer Reviewed
• [Journal Article] Stereoelectronic Effect of Curved Aromatic Structure Favouring the Unexpected Endo Conformation of Benzylic Substituted Sumanene
  • Author(s): S. Higashibayashi, S. Onogi, H. K. Srivastava, G. N. Sastry, Y.-T. Wu, H. Sakurai
  • Journal Title: Angew. Chem. Int. Ed Volume: (in press)
  • DOI: DOI:10.1002/anie.201303134
  • Peer Reviewed
• [Presentation] Chemical Synthesis of Nitrogen-doped Buckybowls (2012)
  • Author(s): Sakurai, H.; Tan, Q.-T.; Higashibayashi, S
  • Organizer: 8th IUPAC International Symposium on Novel Materials and their Synthesis and 22th International Symposium on Fine Chemistry and Functional Polymers
  • Place of Presentation: Xi'an, China
  • Year and Date: 20121014-19
• [Presentation] バッキーボウルにおけるキラリティ (2011)
  • Author(s): 東林修平,櫻井英博
  • Organizer: シンポジウム モレキュラーキラリティ2011
  • Year and Date: 20110520-21
• [Presentation] Bowl Chirality (2010)
  • Author(s): Sakurai, H
  • Organizer: 6th IUPAC International Symposium on Novel Materials and their Synthesis and 20th International Symposium on Fine Chemistry and Functional Polymers
  • Place of Presentation: Wuhan, China
  • Year and Date: 20101010-14
• [Presentation] Asymmetric Synthesis of Chiral Buckybowls (2010)
  • Author(s): Sakurai, H
  • Organizer: Organic Synthesis and Human Well Being: Emerging Opportunities and Challenges
  • Place of Presentation: Hyderabad, India
  • Year and Date: 20100801-04
• [Presentation] Cyclotrimerization of Haloalkenes Catalyzed by Pd Nanoclusters and its Application to Asymmetric Synthesis of Chiral Buckybowls (2010)
  • Author(s): Higashibayashi, S.; Sakurai, H
  • Organizer: Inaugural (1st) International Conference on Molecular & Functional Catalysis
  • Place of Presentation: Singapore, Singapore
  • Year and Date: 20100711-15
• [Presentation] Synthetic Strategy to Construct C3 Symmetric Buckybowls, Bowl-shaped Aromatic Compounds (2010)
  • Author(s): Sakurai, H
  • Organizer: National Organic Symposium Trust XIV Organic Chemistry Conference
  • Place of Presentation: Goa, India
  • Year and Date: 2010-05-08
• [Presentation] Asymmetric Synthesis of Chiral Buckybowls (2009)
  • Author(s): Sakurai, H
  • Organizer: International Symposium on Organic Chemistry; Trends in 21st Century
  • Place of Presentation: Kolkata, India
  • Year and Date: 20091210-12
• [Presentation] Asymmetric Synthesis of a Chiral Buckybowl (2009)
  • Author(s): Sakurai, H
  • Organizer: International Symposium on Chiral Compounds and Special Polymers
  • Place of Presentation: Harbin, China
  • Year and Date: 20090713-16
• [Presentation] 精密有機合成で挑戦するπ共役の次元制御 (2009)
  • Author(s): 櫻井英博
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 船橋
  • Year and Date: 20090327-30
• [Presentation] Asymmetric Synthesis of a Chiral Buckybowl (2009)
  • Author(s): Sakurai, H
  • Organizer: Okazaki Conference 2009
  • Place of Presentation: Okazaki, Japan
  • Year and Date: 20090221-23
• [Book] 精密有機合成によるカーボンπ空間の構築, 高次π空間の創発と機能開発,赤坂健編 (2013)
  • Author(s): 櫻井英博
  • Total Pages: 40-43
  • Publisher: シーエムシー出版
• [Book] 精密合成が拓くπ電子科学, CSJ カレントレビュー12 未来材料を創出するπ電子系の科学-新しい合成・構造・機能化研究,赤坂健,岩澤伸治,山口茂弘、磯部寛之編 (2013)
  • Author(s): 櫻井英博,東林修平
  • Total Pages: 46-53
  • Publisher: 化学同人
• [Remarks]
  • URL: http://groups.ims.ac.jp/organization/sakurai_g/
• [Remarks] 新聞報道
• [Remarks] 科学新聞2012 年6 月29 日1 面
• [Remarks] 日刊工業新聞2012 年6 月20 日21 面